CN102112551B - Thermoplastic articles including polyhydroxy polymers - Google Patents
Thermoplastic articles including polyhydroxy polymers Download PDFInfo
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- CN102112551B CN102112551B CN2009801298212A CN200980129821A CN102112551B CN 102112551 B CN102112551 B CN 102112551B CN 2009801298212 A CN2009801298212 A CN 2009801298212A CN 200980129821 A CN200980129821 A CN 200980129821A CN 102112551 B CN102112551 B CN 102112551B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
Abstract
Disclosed is a molded or extruded thermoplastic article having high heat stability, including a thermoplastic polyamide composition including (a) a polyamide resin; (b) 0.25 to 20 weight percent of one or more polyhydroxy polymer(s) having a number average molecular weight of at least 2000; (c) 0.1 to 3 weight percent of one or more co-stabilizer(s) selected from the group consisting of secondary aryl amines, hindered amine light stabilizers, hindered phenols, and mixtures thereof; (d) 0 to less than 10 weight percent of one or more reinforcement agents; and (e) 0 to 20 weight percent of a polymeric toughener; wherein molded 4 mm test bars prepared from said polyamide composition, and exposed in an oven at an test temperature of at least 150 DEG C for a test period of at least 500 hours, in an atmosphere of air, and tested according to ISO 527-2/1A, have, on average, a retention of elongation at break of at least 50 percent, as compared to that of an unexposed control of identical composition and shape.
Description
the cross reference of related application
Present patent application require to be filed on July 30th, 2008, at present just in the right of priority of the U.S. Provisional Application 61/137,345 of pending trial.
Invention field
The present invention relates to molding that thermostability makes moderate progress and the field of extruded thermoplastic goods.
background of invention
High-temperature resin based on polymeric amide has desired chemical resistant properties, workability and thermotolerance.This makes them be particularly useful for the high high-performance motor vehicle of requirement and electrical/electronic device application.Generally wish to have high-temperature-resistant structure at automotive field at present, because the temperature in the motor vehicle engine chamber region is usually above 150 ℃, even higher than 200 ℃.When plastic components is exposed to this high temperature lower time for a long time, for example, in the application of motor vehicle engine chamber or electrical/electronic device application, due to the thermooxidizing of polymkeric substance, mechanical characteristics is tending towards reducing usually.This phenomenon is called thermal ageing.
In the trial that improves heat aging performance, conventional way is to add thermo-stabilizer (also referred to as antioxidant) in comprising the thermoplastic compounds of polyamide resin.The example of this type thermal stabilizing agent comprises hindered phenol antioxidant, amine antioxidant and phosphorous antioxidant.With regard to daiamid composition, the mechanical characteristics of the composition while usually keeping being exposed to high temperature with the thermo-stabilizer of three types.A kind of is that what to mention in the past is optionally the phenol antioxidant that synergistic agent is combined use with phosphorus, and the second is with phosphorus, to be optionally the aromatic amine that synergistic agent is combined use, and the third is to use mantoquita and derivative.Known phenol antioxidant can improve the machinery/physical property of thermoplastic compounds, can make aging temperature be up to 120 ℃.
Existing technology not only is difficult to improve long-term heat-resistant aging, and the thermal ageing properties of improving are not enough to meet and relate to the higher application of requirement that is exposed to higher temperature, for example the application of motor vehicle engine chamber and electrical/electronic device application.
EP 1041109 discloses daiamid composition, and this daiamid composition comprises polyamide resin and polyvalent alcohol, has the fusing point of 150 to 280 ℃ and good mobility and physical strength, and can be used for the injection moulding welding technique.
Another problem is the heat aging performance that usually has the low levels toughener or do not contain the daiamid composition of toughener.Because the composition do not strengthened is generally used for needing certain flexible application; The important property of the thermoplastics do not strengthened is to keep breaking strain when thermal ageing.
Regrettably, use existing technology, according to have the low levels toughener or not containing the flexible polyamide composition of toughener and the goods of molding otherwise long-term exposure during in high temperature its mechanical characteristics can stand unacceptable deteriorated, or owing to using expensive thermo-stabilizer to make them very expensive.
What still need is the low-cost daiamid composition that is suitable for manufacturing goods and shows good mechanical characteristics after long term high temperature exposes.
Summary of the invention
This paper discloses and is subject to the molding of claims protection or the thermoplastic article of extrusion molding to comprise polyamide thermoplastic compositions, and described polyamide thermoplastic compositions comprises:
(a) there is the polyamide resin of fusing point and/or glass transition point;
(b) one or more polyhydroxylated polymers of 0.25 to 20 % by weight, described polyhydroxylated polymer is selected from ethylene/vinyl alcohol copolymer and poly-(vinyl alcohol) of the number-average molecular weight with at least 2000;
(c) one or more co-stabilizers of 0.1 to 3 % by weight, if the described fusing point of polymeric amide exists, described co-stabilizer has the low 10% weight loss temperature more than 30 ℃ of the described fusing point of ratio of measuring with thermogravimetric analysis, if perhaps described fusing point does not exist, described co-stabilizer has the 10% weight loss temperature of at least 250 ℃, and described one or more co-stabilizers are selected from secondary arylamines, hindered amine as light stabilizer, hindered phenol and their mixture;
(d) 0 to one or more tougheners that are less than 10 % by weight; With
(e) the polymer toughening agent of 0 to 20 % by weight, the metal-salt that described polymer toughening agent comprises active function groups and/or carboxylic acid;
Wherein with the elongation at break that does not expose contrast of same composition and shape, compare, be exposed to air atmosphere under the probe temperature of 150 ℃ within the test duration of 500 hours or approximately 500 hours in, and tested according to ISO 527-2/1A, the 4mm molding test rod prepared by described daiamid composition has average at least 50% reserved elongation at break.
detailed Description Of The Invention
For purposes of illustration, except as otherwise noted, otherwise " high temperature " refer to into or higher than the temperature of 150 ℃.
In the present invention, except as otherwise noted, otherwise " for a long time " refers to the exposure period of 500 hours.
As used herein, when term " high thermal stability " is applied to daiamid composition disclosed herein or during the goods made by said composition, refer to and be exposed to the test duration that hot air box aging (AOA) condition is or is about 500h in air atmosphere under the probe temperature of 150 ℃ in baking oven, then tested the retention rate of the physical property of the thick molding test rod of the 4mm formed by said composition (for example tensile strength) according to ISO 527-2/1A method.The physical property of test rod is compared with the elongation at break that does not expose contrast with same composition and shape, and meaned according to " % reservation "." high thermal stability " herein refer to described molding test rod under being exposed to the probe temperature of 150 ℃ for or on average can meet or exceed 50% reserved elongation at break while being about test duration of 500h.The composition that shows higher building reason characteristic retention rate under the condition of given Exposure Temperature and time period has thermostability preferably.
Term " (methyl) acrylate " is intended to comprise acrylate and methacrylic ester.
The polyamide resin used in the present invention has fusing point and/or glass transition point.In this article, in heat scan for the first time by dsc (DSC) determination of scan rate fusing point and the glass transition point with 10 ℃/minute, the value of wherein getting maximum endotherm(ic)peak place is fusing point, if significantly words are considered as glass transition point by the mid point of enthalpy change.
Polymeric amide is one or more di-carboxylic acid and one or more diamines, and/or one or more aminocarboxylic acids, and/or the condensation product of the ring-opening polymerization product of one or more cyclic lactames.Suitable cyclic lactames is hexanolactam and laurolactam.Polymeric amide can be full-cream family or half aromatics.
Full-cream polyamide used in resin combination of the present invention is formed by aliphatic series and alicyclic monomer, for example diamines, di-carboxylic acid, lactan, aminocarboxylic acid and their reaction equivalent.Suitable aminocarboxylic acid is the amino dodecylic acid of 11-.Suitable lactan is hexanolactam and laurolactam.In the context of the present invention, term " full-cream polyamide " also refers to derived from the multipolymer of two or more these type of monomers and the blend of two or more full-cream polyamides.Can use the monomer of straight chain, side chain and ring-type.
The carboxylic acid monomer who comprises in full-cream polyamide includes but not limited to aliphatic carboxylic acid, for example hexanodioic acid (C6), pimelic acid (C7), suberic acid (C8), nonane diacid (C9), sebacic acid (C10), dodecanedioic acid (C12), undecane dicarboxylic acid (C13), tetradecane diacid (C14) and pentadecane diacid (C15).Diamines can be selected from the diamines with four or more carbon atoms, include but not limited to tetramethylene-diamine, hexamethylene-diamine, 1,8-octamethylenediamine, decamethylene diamine, ten dimethylene diamines, 2 methyl pentamethylenediamine, 2-ethyl tetramethylene-diamine, 2-methyl octamethylenediamine; Trimethylhexamethylenediamine, m-xylene diamine and/or their mixture.
Partially aromatic polyamide serve as reasons homopolymer that the monomer that comprises aryl forms, multipolymer, terpolymer or high polymer more.One or more aromatic carboxylic acids can be the mixtures of terephthalic acid or terephthalic acid and one or more other carboxylic acids, as m-phthalic acid, phthalic acid, 2-methyl terephthalic acid and naphthalic acid.In addition, described one or more aromatic carboxylic acids can mix with one or more aliphatic dicarboxylic acids, as above disclosed.Perhaps, can use the aromatic diamine such as m-xylene diamine (MXD) that partially aromatic polyamide is provided, the example is MXD6, and it is the homopolymer consisted of MXD and hexanodioic acid.
Preferred polyamide disclosed herein is homopolymer or multipolymer, and wherein term " multipolymer " refers to the polymeric amide with two or more acid amides and/or diamide molecule repeating unit.Homopolymer and multipolymer by them repeating unit separately differentiated.For multipolymer disclosed herein, repeating unit based on them the order % by mole from high to low in multipolymer list.Following list exemplarily shows for meaning homopolymer and the monomer of multipolymer polymeric amide (PA) and the abbreviation of repeating unit:
HMD hexamethylene-diamine while using together with diacid (or be 6)
The T terephthalic acid
The AA hexanodioic acid
The DMD decamethylene diamine
6
-hexanolactam
The DDA sebacic acid
The DDDA dodecanedioic acid
The I m-phthalic acid
The MXD m-xylene diamine
TMD Isosorbide-5-Nitrae-tetramethylene-diamine
The polymer repeat unit that 4T is formed by TMD and T
The polymer repeat unit that 6T is formed by HMD and T
The polymer repeat unit that DT is formed by 2-MPMD and T
The polymer repeat unit that MXD6 is formed by MXD and AA
66 polymer repeat units that formed by HMD and AA
The polymer repeat unit that 10T is formed by DMD and T
410 polymer repeat units that formed by TMD and DDA
510 polymer repeat units that formed by 1,5-pentamethylene diamine and DDA
610 polymer repeat units that formed by HMD or DDA
612 polymer repeat units that formed by HMD and DDDA
6 by
the polymer repeat unit that-hexanolactam forms
11 polymer repeat units that formed by the amino undecanoic acid of 11-
12 polymer repeat units that formed by 12 amino dodecanoic acid
Note, in the art, when term " 6 " while using separately, refer to by
the polymer repeat unit that-hexanolactam forms.Perhaps, when " 6 ", when using together with diacid such as T, as 6T, " 6 " refer to HMD.In the repeating unit that comprises diamines and diacid, at first name diamines.In addition, when " 6 " are used together with diamines, as 66, first " 6 " refer to diamines HMD, and second " 6 " refer to hexanodioic acid.Equally, derived from the repeating unit of other amino acid or lactan, with the individual digit that means amount of carbon atom, name.
In one embodiment, daiamid composition comprises one or more and is selected from following polymeric amide:
(I) organizes polymeric amide, and it has the described fusing point that is less than 210 ℃, and comprises and be selected from following aliphatic series or partially aromatic polyamide: poly-(sebacoyl pentamethylene diamine) (PA510), gather (dodecane two acyl pentamethylene diamines) (PA512), gather (ε-caprolactam/hexamethylene adipamide) (PA6/66), gather (ε-caprolactam/sebacoyl hexanediamine) (PA6/610), gather (ε-caprolactam/dodecane two acyl hexanediamines) (PA6/612), gather (tridecane two acyl hexanediamines) (PA613), gather (pentadecane two acyl hexanediamines) (PA615), gather (ε-caprolactam/paraphenylene terephthalamide's butanediamine) (PA6/4T), gather (ε-caprolactam/hexamethylene terephthalamide) (PA6/6T), gather (ε-caprolactam/paraphenylene terephthalamide's decamethylene diamine) (PA6/10T), gather (ε-caprolactam/paraphenylene terephthalamide's 12 carbon diamines) (PA6/12T), gather (sebacoyl hexanediamine/hexamethylene terephthalamide) (PA610/6T), gather (dodecane two acyl hexanediamine/hexamethylene terephthalamides) (PA612/6T), gather (tetradecane two acyl hexanediamine/hexamethylene terephthalamides) (PA614/6T), gather (ε-caprolactam/6I hexamethylene isoterephalamide/hexamethylene terephthalamide) (PA6/6I/6T), gather (ε-caprolactam/hexamethylene adipamide/sebacoyl hexanediamine) (PA6/66/610), gather (ε-caprolactam/hexamethylene adipamide/dodecane two acyl hexanediamines) (PA6/66/612), gather (ε-caprolactam/hexamethylene adipamide/sebacoyl hexanediamine/dodecane two acyl hexanediamines) (PA6/66/610/612), poly-(hexanedioyl 2 methyl pentamethylenediamine/hexamethylene adipamide/hexamethylene terephthalamide) (PA D6/66//6T), poly-(hexanedioyl 2 methyl pentamethylenediamine/hexamethylene adipamide /) (PA D6/66), gather (sebacoyl decamethylene diamine) (PA1010), gather (dodecane two acyl decamethylene diamines) (PA1012), gather (sebacoyl decamethylene diamine/paraphenylene terephthalamide's decamethylene diamine) (PA1010/10T), poly-(sebacoyl decamethylene diamine/sebacoyl 12 carbon diamines/paraphenylene terephthalamide decamethylene diamine/paraphenylene terephthalamide 12 carbon diamines (PA1010/1210/10T/12T), gather (the amino undecanoic amide of 11-) (PA11), gather (the amino undecanoic amide of 11-/paraphenylene terephthalamide's butanediamine) (PA11/4T), gather (the amino undecanoic amide/hexamethylene terephthalamide of 11-) (PA11/6T), gather (the amino undecanoic amide of 11-/paraphenylene terephthalamide's decamethylene diamine) (PA11/10T), gather (the amino undecanoic amide/paraphenylene terephthalamide's 12 carbon diamines of 11-) (PA11/12T), gather (the amino dodecane acid amides of 12-) (PA12), gather (the amino dodecane acid amides of 12-/paraphenylene terephthalamide's butanediamine) (PA12/4T), gather (the amino dodecane acid amides/hexamethylene terephthalamide of 12-) (PA12/6T), gather (the amino dodecane acid amides of 12-/paraphenylene terephthalamide's decamethylene diamine) (PA12/10T), gather (dodecane two acyl 12 carbon diamines) (PA1212), and poly-(dodecane two acyl 12 carbon diamines/dodecane two acyl 12 carbon diamines/paraphenylene terephthalamide 12 carbon diamines) (PA1212/12T),
(II) organizes polymeric amide, it has the described fusing point of at least 210 ℃, and comprise and be selected from following aliphatic polyamide: poly-(hexanedioyl butanediamine) (PA46), poly-(ε-caprolactam) (PA 6), poly-(hexamethylene adipamide/(ε-caprolactam /) (PA 66/6), poly-(hexamethylene adipamide) (PA 66), gather (hexamethylene adipamide/sebacoyl hexanediamine) (PA66/610), gather (hexamethylene adipamide/dodecane two acyl hexanediamines) (PA66/612), gather (hexamethylene adipamide/sebacoyl decamethylene diamine) (PA66/1010), gather (sebacoyl hexanediamine) (PA610), gather (dodecane two acyl hexanediamines) (PA612), gather (tetradecane two acyl hexanediamines) (PA614), gather (n-Hexadecane two acyl hexanediamines) (PA616), and poly-(hexanedioyl butanediamine/hexanedioyl 2 methyl pentamethylenediamine) (PA46/D6),
(III) organizes polymeric amide, and it has the described fusing point of at least 210 ℃, and comprises
(aa), approximately 20 to about half aromatic repeating units of 35 % by mole, described half aromatic repeating units is derived from being selected from following one or more monomer:
(i) there is the aromatic dicarboxylate and the aliphatic diamine with 4 to 20 carbon atoms of 8 to 20 carbon atoms; With
(bb), approximately 65 to the about aliphatic repeating unit of 80 % by mole, described aliphatic repeating unit is derived from being selected from following one or more monomer:
(ii) there is the aliphatic dicarboxylic acid and the described aliphatic diamine with 4 to 20 carbon atoms of 6 to 20 carbon atoms; With
(iii) there is lactan and/or the aminocarboxylic acid of 4 to 20 carbon atoms;
(IV) organizes polymeric amide, and it comprises
(cc), approximately 50 to about half aromatic repeating units of 95 % by mole, described half aromatic repeating units is derived from being selected from following one or more monomer:
(i) there is the aromatic dicarboxylate and the aliphatic diamine with 4 to 20 carbon atoms of 8 to 20 carbon atoms; With
(dd), approximately 5 to the about aliphatic repeating unit of 50 % by mole, described aliphatic repeating unit is derived from being selected from following one or more monomer:
(ii) there is the aliphatic dicarboxylic acid and the described aliphatic diamine with 4 to 20 carbon atoms of 6 to 20 carbon atoms; And
(iii) there is lactan and/or the aminocarboxylic acid of 4 to 20 carbon atoms;
(V) organizes polymeric amide, and it has the described fusing point of at least 260 ℃, and comprises
(ee) be greater than half aromatic repeating units of 95 % by mole, described half aromatic repeating units is derived from being selected from following one or more monomer:
(i) there is the aromatic dicarboxylate and the aliphatic diamine with 4 to 20 carbon atoms of 8 to 20 carbon atoms; And
(ff) be less than the aliphatic repeating unit of 5 % by mole, described aliphatic repeating unit is derived from being selected from following one or more monomer:
(ii) there is the aliphatic dicarboxylic acid and the described aliphatic diamine with 4 to 20 carbon atoms of 6 to 20 carbon atoms;
(iii) there is lactan and/or the aminocarboxylic acid of 4 to 20 carbon atoms; With
(VI) organizes polymeric amide, it does not have fusing point, and be selected from poly-(6I hexamethylene isoterephalamide/hexamethylene terephthalamide) (6I/6T) and poly-(6I hexamethylene isoterephalamide/hexamethylene terephthalamide/hexamethylene adipamide) (6I/6T/66).
The content of half aromatic repeating units in (I) group polymeric amide should make fusing point be less than 210 ℃, and this group partially aromatic polyamide has half aromatic repeating units that is less than 40 % by mole usually.Half aromatic repeating units is defined as derived from being selected from following one or more those half aromatic repeating units of monomer: the aliphatic diamine that has the aromatic dicarboxylate of 8 to 20 carbon atoms and have 4 to 20 carbon atoms.
An embodiment is the thermoplastic article of molding or extrusion molding, and wherein said polyamide resin is selected from (II) group polymeric amide.
Another embodiment is the thermoplastic article of molding or extrusion molding, wherein said polyamide resin is selected from (III) group polymeric amide, this group polymeric amide is selected from poly-(hexanedioyl butanediamine/paraphenylene terephthalamide's butanediamine) (PA46/4T), gather (hexanedioyl butanediamine/hexamethylene terephthalamide) (PA46/6T), gather (hexanedioyl butanediamine/hexanedioyl 2 methyl pentamethylenediamine/paraphenylene terephthalamide's decamethylene diamine) (PA46/D6/10T), gather (hexamethylene adipamide/hexamethylene terephthalamide) (PA66/6T), gather (hexamethylene adipamide/6I hexamethylene isoterephalamide/hexamethylene terephthalamide) (PA66/6I/6T), and poly-(hexamethylene adipamide/hexanedioyl 2 methyl pentamethylenediamine/hexamethylene terephthalamide) (PA66/D6/6T).Most preferred (III) group polymeric amide is PA66/6T.
Another embodiment is the thermoplastic article of molding or extrusion molding, and wherein said polyamide resin is selected from (IV) group polymeric amide, and this group polymeric amide is selected from poly-(paraphenylene terephthalamide's butanediamine/hexamethylene adipamide) (PA4T/66), gather (paraphenylene terephthalamide's butanediamine/ε-caprolactam) (PA4T/6), gather (paraphenylene terephthalamide's butanediamine/dodecane two acyl hexanediamines) (PA4T/612), gather (paraphenylene terephthalamide's butanediamine/hexanedioyl 2 methyl pentamethylenediamine/hexamethylene adipamide) (PA4T/D6/66), gather (hexamethylene terephthalamide/paraphenylene terephthalamide's 2 methyl pentamethylenediamine/hexamethylene adipamide) (PA6T/DT/66), poly-(hexamethylene terephthalamide/hexamethylene adipamide) PA6T/66, gather (hexamethylene terephthalamide/sebacoyl hexanediamine) (PA6T/610), gather (hexamethylene terephthalamide/tetradecane two acyl hexanediamines) (PA6T/614), gather (paraphenylene terephthalamide's nonamethylene diamine/sebacoyl nonamethylene diamine) (PA9T/910), gather (paraphenylene terephthalamide's nonamethylene diamine/dodecane two acyl nonamethylene diamines) (PA9T/912), gather (the amino undecanoic amide of paraphenylene terephthalamide's nonamethylene diamine/11-) (PA9T/11), gather (the amino dodecane acid amides of paraphenylene terephthalamide's nonamethylene diamine/12-) (PA9T/12), poly-(the amino undecanoic amide of paraphenylene terephthalamide's decamethylene diamine/11-) (PA 10T/11), gather (the amino dodecane acid amides of paraphenylene terephthalamide's decamethylene diamine/12-) (PA10T/12), gather (paraphenylene terephthalamide's decamethylene diamine/sebacoyl decamethylene diamine) (PA10T/1010), gather (paraphenylene terephthalamide's decamethylene diamine/dodecane two acyl decamethylene diamines) (PA10T/1012), gather (paraphenylene terephthalamide's decamethylene diamine/hexanedioyl butanediamine) (PA10T/46), gather (paraphenylene terephthalamide's decamethylene diamine/ε-caprolactam) (PA10T/6), gather (paraphenylene terephthalamide's decamethylene diamine/hexamethylene adipamide) (PA10T/66), gather (paraphenylene terephthalamide's 12 carbon diamines/dodecane two acyl 12 carbon diamines) (PA12T/1212), gather (paraphenylene terephthalamide's 12 carbon diamines/ε-caprolactam) (PA12T/6), and poly-(paraphenylene terephthalamide's 12 carbon diamines/hexamethylene adipamides) (PA12T/66), most preferred (IV) group polymeric amide is PA6T/66.
Another embodiment is the thermoplastic article of molding or extrusion molding, wherein said polyamide resin is selected from (V) group polymeric amide, this group polymeric amide is selected from poly-(paraphenylene terephthalamide's butanediamine/paraphenylene terephthalamide's 2 methyl pentamethylenediamine) PA4T/DT, poly-(paraphenylene terephthalamide's butanediamine/hexamethylene terephthalamide) PA4T/6T, poly-(paraphenylene terephthalamide's butanediamine/paraphenylene terephthalamide's decamethylene diamine) PA4T/10T, poly-(paraphenylene terephthalamide butanediamine/paraphenylene terephthalamide 12 carbon diamines) PA4T/12T, gather (paraphenylene terephthalamide's butanediamine/paraphenylene terephthalamide's 2 methyl pentamethylenediamine/hexamethylene terephthalamide) (PA4T/DT/6T), gather (paraphenylene terephthalamide's butanediamine/hexamethylene terephthalamide/paraphenylene terephthalamide's 2 methyl pentamethylenediamine) (PA4T/6T/DT), gather (hexamethylene terephthalamide/paraphenylene terephthalamide's 2 methyl pentamethylenediamine) (PA6T/DT), poly-(hexamethylene adipamide/6I hexamethylene isoterephalamide) (PA 6T/6I), poly-(hexamethylene terephthalamide/paraphenylene terephthalamide's decamethylene diamine) PA6T/10T, gather (hexamethylene terephthalamide/paraphenylene terephthalamide's 12 carbon diamines) (PA6T/12T), it is poly-that (hexamethylene terephthalamide/paraphenylene terephthalamide's 2 methyl pentamethylenediamine/poly-(paraphenylene terephthalamide's decamethylene diamine) (PA6T/DT/10T), gather (hexamethylene terephthalamide/paraphenylene terephthalamide decamethylene diamine/paraphenylene terephthalamide 12 carbon diamines) (PA6T/10T/12T), gather (paraphenylene terephthalamide's decamethylene diamine) (PA10T), gather (paraphenylene terephthalamide's decamethylene diamine/paraphenylene terephthalamide's butanediamine) (PA10T/4T), gather (paraphenylene terephthalamide's decamethylene diamine/paraphenylene terephthalamide's 2 methyl pentamethylenediamine) (PA10T/DT), gather (paraphenylene terephthalamide decamethylene diamine/paraphenylene terephthalamide 12 carbon diamines) (PA10T/12T), it is poly-that (paraphenylene terephthalamide's decamethylene diamine/paraphenylene terephthalamide's 2 methyl pentamethylenediamine/(paraphenylene terephthalamide's decamethylene diamine) (PA10T/DT/12T).Poly-(paraphenylene terephthalamide's 12 carbon diamines) (PA12T), poly-(paraphenylene terephthalamide's 12 carbon diamines)/paraphenylene terephthalamide's butanediamine) (PA12T/4T), poly-(paraphenylene terephthalamide's 12 carbon diamines)/hexamethylene terephthalamide) PA12T/6T, poly-(paraphenylene terephthalamide's 12 carbon diamines)/paraphenylene terephthalamide's decamethylene diamine) (PA12T/10T) and poly-(paraphenylene terephthalamide's 12 carbon diamines)/paraphenylene terephthalamide's 2 methyl pentamethylenediamine) (PA12T/DT); Most preferred (V) group polymeric amide is PA6T/DT.
Another preferred embodiment is the thermoplastic article of molding or extrusion molding, wherein said polyamide resin is selected from (V) group polymeric amide, wherein the not exposure contrast identical with shape with composition compared, and described reserved elongation at break is at least 70%, and more preferably at least 80% and 90%.
In a plurality of embodiments, polymeric amide is respectively (I) group polymeric amide, (II) group polymeric amide, (III) group polymeric amide, (IV) group polymeric amide, (V) group polymeric amide or (VI) group polymeric amide.
Polymeric amide can be also the blend of two or more polymeric amide.Preferred blend comprises those that are selected from following group: (I) group and (II) group polymeric amide; (I) group and (III) group polymeric amide, (I) group and (VI) group polymeric amide, (II) group and (III) group polymeric amide, (II) group and (IV) group polymeric amide, (II) group and (V) group polymeric amide, (II) group and (VI) group polymeric amide, (III) group and (VI) group polymeric amide and (IV) group and (V) group polymeric amide.
Preferred blend comprises (II) group and (V) group polymeric amide, and particularly preferred blend comprises poly-(hexamethylene adipamide) (PA 66) and poly-(hexamethylene terephthalamide/paraphenylene terephthalamide's 2 methyl pentamethylenediamine) (PA 6T/DT).
Another kind of preferred blend comprises (II) group and (III) group polymeric amide, and particularly preferred blend comprises poly-(ε-caprolactam) (PA6) and poly-(hexamethylene adipamide/hexamethylene terephthalamide (PA66/6T).
At least one polyhydroxylated polymer that the thermoplastic article of molding or extrusion molding comprises 0.25 to 20 % by weight, described polyhydroxylated polymer is selected from the number-average molecular weight (M with at least 2000
n) ethylene/vinyl alcohol copolymer and poly-(vinyl alcohol); Described gel permeation chromatography (GPC) mensuration polymeric material acquisition for number-average molecular weight.Preferably, polyhydroxylated polymer has 5000 to 50,000 M
n.
In one embodiment, polyhydroxylated polymer is ethylene/vinyl alcohol copolymer (EVOH).EVOH can have the vinyl alcohol repeating unit content of 10 to 90 % by mole, preferably 30 to 80 % by mole, 40 to 75 % by mole, 50 to 75 % by mole and 50 to 60 % by mole, and wherein remaining % by mole is ethylene repeating unit content.Be applicable to the EVOH of thermoplastic compounds for deriving from the Soarnol of Nippon Gosei (Tokyo, Japan)
a or D multipolymer and the EVAL that derives from Kuraray (Tokyo, Japan)
multipolymer.
In one embodiment, polyhydroxylated polymer is poly-(vinyl alcohol) polymkeric substance (PVOH).The PVOH polymkeric substance that is applicable to thermoplastic compounds is the Mowiol that derives from Kuraray Europe Gmbh
the board resin.
By the gross weight of polyamide thermoplastic compositions, the thermoplastic article of molding or extrusion molding can comprise 1 to 15 % by weight, 1 to 10 % by weight; Preferred 1 to 7 % by weight, and the more preferably polyhydroxylated polymer of 2 to 7 % by weight.
With there is the M that is less than 2000
npolyvalent alcohol (for example Dipentaerythritol) compare, use and to have at least 2000 or higher M
npolyhydroxylated polymer especially contribute to improve the thermostability of daiamid composition.The polyhydroxylated polymer composition is in long-term exposure during in high temperature, and polymkeric substance is tending towards lower in molding or extrudate lip-deep " frosting " speed.Many low molecular weight additives have from the teeth outwards the trend of " frosting " or migration crystallization during in high temperature in long-term exposure, thereby form worthless surperficial whiting.In addition, the polyhydroxylated polymer such as EVOH has overall better thermostability than low molecular weight polyols.For example, while scanning under up to 350 ℃, EVOH has TGA (sweep velocitys of 10 ℃/minute) weight loss of 1.9 % by weight; And Dipentaerythritol has 70% weight loss under the same conditions.
One or more co-stabilizers that daiamid composition comprises 0.1 to 3 % by weight, the fusing point that described co-stabilizer has the ratio polyamide resin of measuring by thermogravimetric analysis (TGA) method is low more than 30 ℃ (if fusing point existence), be perhaps the 10% weight loss temperature of at least 250 ℃ (if the non-existent words of described fusing point), described one or more co-stabilizers are selected from secondary arylamines, hindered phenol and hindered amine as light stabilizer (HALS) and their mixture.
For purposes of the present invention, will, according to ASTM D 3850-94, by the heating rate of 10 ℃/minute, in the purifying air stream of the proper flow rates of 0.8 milliliters/second, measure TGA weight loss.Described one or more co-stabilizers preferably have the 10% weight loss temperature of at least 270 ℃ of measuring with TGA, and more preferably 290 ℃, 320 ℃ and 340 ℃, and most preferably be at least 350 ℃.
By the gross weight of daiamid composition, the content of described one or more co-stabilizers is preferably or is about 0.1 most or be about 3 % by weight, more preferably or be about 0.1 most or be about 1 % by weight; Or more preferably or be about 0.1 most or be about 0.7 % by weight.
Can be used for secondary arylamines of the present invention is the high molecular organic compound with low volatility.The high molecular organic compound is preferably selected from secondary arylamines, this, arylamines feature also was to have at least 260g/mol second month in a season, the preferred at least molecular weight of 350g/mol, and at least 290 ℃ of measuring with thermogravimetric analysis (TGA), preferably at least 300 ℃, 320 ℃, 340 ℃, and the 10% weight loss temperature of at least 350 ℃ most preferably.
So-called secondary arylamines refers to and comprises two substituent aminocompounds that are chemically bonded on nitrogen-atoms, at least one substituting group wherein, and preferably two substituting groups are aromatics.Preferably can preferably be comprised 1 by least one such as at least one in the aromatic substituent of phenyl, naphthyl or heteroaryl replaces to the about substituting group of 20 carbon atoms.
The example of suitable secondary arylamines comprises 4,4 ' bis-(alpha, alpha-dimethylbenzyl) pentanoic, can Naugard 445 commercially available from Uniroyal Chemical Company (Middlebury, Conn.); The secondary arylamines condensation reaction products of pentanoic and acetone, can Aminox commercially available from Uniroyal Chemical Company; And p-(tolysulfonyl amido) pentanoic, can derive from Uniroyal Chemical Company by Naugard SA.Other suitable secondary arylaminess comprise N, and N '-bis--(2-naphthyl)-Ursol D, derive from ICI Rubber Chemicals (Calcutta, India).Other suitable secondary arylaminess comprise 4,4 '-bis-(α, α '-tertiary octyl group) pentanoic, 4, and 4 '-bis-(Alpha-Methyl diphenyl-methyl) pentanoic, and other are from the secondary arylamines of EP 0509282B1.Preferred co-stabilizer for daiamid composition is secondary arylamines.
So-called hindered phenol refers to the organic compound that comprises at least one phenolic group, and wherein the aromatics part can be at least one, preferably at least two positions with the carbon direct neighbor are substituted, and wherein carbon has as substituent phenolic hydroxyl group.The substituting group adjacent with hydroxyl is alkyl, can suitably be selected from the alkyl with 1 to 10 carbon atom, is preferably the tertiary butyl.The molecular weight of hindered phenol suitably is at least about 260, is preferably at least about 500, more preferably at least about 600.Most preferred for especially to there is the hindered phenol of low volatility under molding is filled a prescription processing temperature used, be further characterized in that and there are at least 290 ℃, preferably at least 300 ℃, 320 ℃, 340 ℃, the 10%TGA weight loss temperature of at least 350 ℃ most preferably.
Suitable hindered phenol compound comprises for example four (methylene radical (3,5-bis--(uncle)-butyl-4-hydroxyl hydrogenated cinnamate)) methane, can Irganox
1010 is commercially available from CIBA Specialty Chemicals (Tarrytown, N.Y.); And N, N '-hexa-methylene two (3,5-bis--(uncle) butyl-hydroxyl hydrocinnamamide), can Irganox
1098 derive from CIBA Specialty Chemicals.Other suitable hindered phenols comprise 1,3,5-trimethylammonium-2,4, and 6-tri-(3,5-bis--(uncle)-butyl-4-hydroxybenzyl) benzene and 1,6-hexa-methylene two (3,5-bis--(uncle) butyl-4-hydroxyl hydrogenated cinnamate), respectively with Irganox
1330 and 259 derive from CIBA Specialty Chemicals.Preferred co-stabilizer for daiamid composition is hindered phenol.Irganox 1098 is the most preferably hindered phenol for said composition.
Hindered amine as light stabilizer (HALS) can be one or more hindered amine type light stabilizer (HALS).
HALS has the compound of following general formula and their combination:
In these general formulas, R
1to R
5(comprise R
5) be substituting group independently.Suitable substituent example is hydrogen, ether, ester group, amido, amide group, alkyl, thiazolinyl, alkynyl, aralkyl, cycloalkyl and aryl, and wherein said substituting group can comprise functional group then; Described functional group example is alcohol, ketone, acid anhydrides, imines, siloxanes, ether, carboxyl, aldehyde, ester, acid amides, imide, amine, nitrile, ether, urethane and their any combination.Hindered amine as light stabilizer also can form the part of polymkeric substance or oligopolymer.
HALS is preferably the compound derived from the piperidine compounds replaced, and is the compound of the alkoxyl group piperidinyl compounds of any piperidyl, piperidyl or Piperazinone compounds replaced derived from alkyl and replacement specifically.The example of this compounds is: 2,2,6,6-tetramethyl-4-piperidones; 2,2,6,6-tetramethyl-4-piperidine alcohols; Two-(1,2,2,6,6-pentamethyl piperidyl)-(3 ', 5 '-bis--tert-butyl-4 '-hydroxybenzyl) the butylmalonic acid ester; Two-(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin
770, MW 481); N-(2-hydroxyethyl)-2,2,6, the oligomer (Tinuvin of 6-tetramethyl-4-piperidine alcohols and butanedioic acid
622); Cyanuric acid and N, the oligomer of N-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene diamine; Two-(2,2,6,6-tetramethyl-4-piperidyl) succinates; Two-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin
123); Two-(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (Tinuvin
765); Tinuvin
144; Tinuvin
XT850; Four-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters; N, N '-bis--(2,2,6,6-tetramethyl-4-piperidyl)-hexane-1,6-diamines (Chimasorb
T5); N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; 2,2 '-[(2,2,6,6-tetramethyl-4-piperidyl)-imino group]-bis--[ethanol]; Poly-((6-morpholine-S-triazine-2,4-bis-bases) (2,2,6,6-tetramethyl-4-piperidyl)-imino group hexa-methylene-(2,2,6,6-tetramethyl-4-piperidyl)-imino group) (Cyasorb
UV 3346); 5-(2,2,6,6-tetramethyl-4-piperidyl)-2-ring-undecyl-oxazoles) (Hostavin
N20); 1,1 '-(1,2-ethane-bis--yl)-bis--(3,3 ', 5,5 '-tetramethyl-piperazinones); 8-acetyl group-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-thriazaspiro (4,5) decane-2,4-diones; Poly-methyl-propyl-3-oxygen base-[4 (2,2,6,6-tetramethyl)-piperidyl] siloxanes (Uvasil
299); 1,2,3,4-butane-tetracarboxylic acid-1,2,3-tri-(1,2,2,6,6-pentamethyl-4-piperidyl)-4-tridecyl ester; The copolymer of AMS-N-(2,2,6,6-tetramethyl-4-piperidyl) maleimide and N-stearyl maleimide; 1,2,3,4-BTCA and β, β, β ', β '-tetramethyl-2,4,8,10-tetra-oxaspiros [5.5] hendecane-3,9-diethanol, 1,2,2,6, the polymer (Mark of 6-pentamethyl-4-piperidyl ester
LA63); β, β, β ', β '-tetramethyl-2,4,8,10-tetra-oxaspiros [5.5] hendecane-3,9-diethanol and 1,2,3,4-BTCA, 2,2,6, the polymer (Mark of 6-tetramethyl-4-piperidyl ester
LA68); 1,3:2,4-bis--O-(2,2,6,6-tetramethyl-4-piperidylidene)-D-Glucose alcohol (HALS 7); 7-oxa--3,20-diaza two spiral shells [5.1.11.2]-heneicosane-21-ketone-2,2,4, the oligomer (Hostavin of 4-tetramethyl-20-(oxiranylmethyl radical)
N30); Malonic acid [(4-anisyl) methylene]-bis-(1,2,2,6,6-pentamethyl-4-piperidyl) ester (Sanduvor
PR 31); N, N '-1,6-hexane two bases two [N-(2,2,6,6-tetramethyl-4-piperidyl methyl acid amides (Uvinul
4050H); N, N " '-[1,2-ethane, two bases two [[[4,6-bis-[butyl (1; 2,2,6,6-pentamethyl-4-piperidyl) amino]-1; 3,5-triazine-2-yl] imino group]-3,1-glyceryl]]-bis-[N ', N " dibutyl-N ', N " bis-(1,2,2; 6,6-pentamethyl-4-piperidyl)-1,3; 5-triazine-2,4,6-triamine (Chimassorb
119MW 2286); Poly-[[6-[(1,1,3,33-tetramethyl butyl) amino]-1,3,5-triazine-2,4-bis-bases] [(2,2,6,6-tetramethyl-4-piperidyl)-imino group]-1,6-hexane two bases [(2,2,6,6-tetramethyl-4-piperidyl) imino group]] (Chimassorb
944MW 2000-3000); 1,5-dioxo spiro (5,5) hendecane 3,3-dicarboxylic acids two (2,2,6,6-tetramethyl-4-pyridine radicals) ester (Cyasorb
UV-500); 1,5-dioxo spiro (5,5) hendecane 3,3-dicarboxylic acids two (1,2,2,6,6-pentamethyl-4-pyridine radicals) ester (Cyasorb
UV-516); N-2,2,6,6-tetramethyl-4-piperidyl-N-amino-oxamides; 4-acryloxy-1,2,2,6,6-pentamethyl-4-piperidines; 1,5,8,12-tetra-[2 ', 4 '-bis-(1 ", 2 ", 2 " and, 6 ", 6 " pentamethyl-4 "-piperidyl (butyl) amino)-1 ', 3 ', 5 '-triazine-6 '-yl]-1,5,8,12-tetra-azepine decane; HALS PB-41 (Clariant Huningue S.A.); Nylostab
S-EED (Clariant Huningue S.A.); 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidines-2, the 5-diketone; Uvasorb
HA88; 1,1 '-(1,2-ethane-bis--yl)-bis--(3,3 ', 5,5 '-tetra--methyl-piperazinones) (Good-rite
3034); 1,1 ' 1 " (1,3,5-triazines-2,4,6-tri-bases three (cyclohexyl imino group)-2,1-second two bases) three (3,3,5,5-tetramethyl piperazinones) (Good-rite
3150); And 1,1 ', 1 " (1,3,5-triazines-2,4,6-tri-bases three (cyclohexyl imino group)-2,1-second two bases) three (3,3,4,5,5-tetramethyl piperazinones) (Good-rite
3159).Tinuvin
and Chimassorb
material can derive from Ciba Specialty Chemicals; Cyasorb
material can derive from Cytec Technology Corp.; Uvasil
material can derive from Great Lakes Chemical Corp.; Saduvor
, Hostavin
and Nylostab
material can derive from Clariant Corp.; Uvinul
material can derive from BASF; Uvasorb
material can derive from Partecipazioni Industriali; And Good-rite
material can derive from B.F.Goodrich Co..Mark
material can derive from Asahi Denka Co..
Preferred co-stabilizer for polyamide thermoplastic compositions is HALS.Preferred HALS comprises having and is greater than approximately 1000, is preferably greater than approximately the oligomeric or polymerization HALS of the high molecular of 2000 molecular weight.
Other concrete HALS are selected from two-(2,2,6,6-tetramethyl--4-piperidyl) sebate (Tinuvin
770, MW 481) Nylostab
s-EED (Clariant Huningue S.A.); N, N " '-[1,2-ethane, two bases two [[[4,6-bis-[butyl (1; 2,2,6,6-pentamethyl--4-piperidyl) amino]-1; 3,5-triazine-2-yl] imino-]-3,1-glyceryl]]-bis-[N ', N " dibutyl-N ', N " bis-(1,2,2; 6,6-pentamethyl--4-piperidyl)-1,3; 5-triazine-2,4,6-triamine (Chimassorb
119MW 2286); With poly-[[6-[(1,1,3,33-tetramethyl butyl) amino]-1,3,5-triazine-2,4-bis-bases] [(2,2,6,6-tetramethyl--4-piperidyl)-imino-]-1,6-hexane two bases [(2,2,6,6-tetramethyl--4-piperidyl) imino-]] (Chimassorb
944MW 2000-3000).
Can use the mixture of secondary arylamines and HALS.Preferred embodiment comprises at least two kinds of co-stabilizers, and at least one is selected from secondary arylamines; And at least one is selected from above-disclosed HALS, wherein the total weight percent of co-stabilizer mixture is at least 0.5 % by weight, is preferably at least 0.9 % by weight.
The thermoplastic article of molding or extrusion molding comprises 0 to being less than 10 % by weight, preferably 5 % by weight or one or more tougheners still less.In a preferred embodiment, the thermoplastic article of molding or extrusion molding does not comprise toughener.When having toughener, it can be any filler, but is preferably selected from calcium carbonate, has glass fibre, sheet glass, granulated glass sphere, carbon fiber, talcum, mica, wollastonite, calcined clay, kaolin, diatomite, sal epsom, Magnesium Silicate q-agent, barium sulfate, titanium dioxide, sodium carbonate aluminium, barium ferrite, potassium titanate and their mixture of circle and non-circular cross sections.
The thermoplastic article of molding or extrusion molding optionally comprises the polymerization toughner of the metal-salt with active function groups and/or carboxylic acid of 0 to 50 % by weight.In one embodiment, the polymerization toughner that the thermoplastic article of molding or extrusion molding comprises 2 to 20 % by weight, described polymer toughening agent is selected from: the multipolymer of ethene, (methyl) glycidyl acrylate and optional one or more (methyl) acrylate; Ethylene/alpha-olefin or ethylene/alpha-olefin/diene interpolymers with the unsaturated carboxylic acid anhydrides grafting; The multipolymer of ethene, (methyl) vinylformic acid 2-isocyanato ethyl and optional one or more (methyl) acrylate; And react to generate corresponding ionomeric ethene and acrylic acid multipolymer with zinc, lithium, magnesium or manganic compound.
In the present invention, daiamid composition can also comprise this area other additives commonly used, for example other thermo-stabilizers or antioxidant, antistatic agent, whipping agent, lubricant, softening agent and tinting material and pigment.
Other thermo-stabilizers comprise copper stablizer and their mixture.
The remarkable advantage of molding of the present invention or extruded thermoplastic goods is without using conventional copper thermo-stabilizer just can obtain the thermostability of height.The copper thermo-stabilizer often plays a part etching reagent under long term high temperature; Can actually cause the degraded of half aromatic(based)polymer in some environment.Therefore, the thermoplastic article that another embodiment is molding or extrusion molding, wherein said daiamid composition comprises the copper that is less than 25ppm with Atomic Absorption Spectrometry.
The daiamid composition of this paper is the mixture of melt blending gained, and wherein all polymerization compositions are fully mixed, and all non-polymeric compositions are well dispersed in polymeric matrix.Can mix polymerization composition of the present invention and non-polymeric composition by any melt-mixing method.For example, the polymerization composition can be become be distributed in the melting agitator with non-polymeric, as single screw extrusion machine or twin screw extruder, agitator, single screw rod or Dual-screw kneader or Banbury mixer, in adding step, can add or progressively add in batches all the components is disposable.When progressively adding polymerization composition and non-polymeric composition in batches, the part that can at first add polymerization composition and/or non-polymeric composition, then by itself and follow-up remaining polymerization composition added and non-polymeric composition melting mixing, until obtain well-mixed composition.For example, if reinforcing filler has microscler physical form (long glass fibres), the composition that can use the preparation of stretching extrusion molding to strengthen.
As disclosed, the daiamid composition that has a polyhydroxylated polymer can be used for improving molding or the extrudate long-term thermal stability at high temperature made from it.Can by for or be about in test duration of 500 hours the long-term thermal stability that (being that hot air box is aging) under the probe temperature that by 4mm thick test sample is exposed to 150 ℃ estimates goods.Tensile strength and the elongation at break of the test rod after aging according to ISO 527-2/1A testing method test hot air box; And with there is comparing for the not exposure contrast of dry state mo(u)lded item (DAM) of same composition and shape.Relatively provide tensile strength retention rate and/or reserved elongation at break with the DAM contrast, thereby can estimate the long-term thermal stability energy of multiple combination thing.
In a plurality of embodiments, according to DAM, not exposing the comparison of contrast, polyamide thermoplastic compositions has at least 50% tensile strength retention rate under the AOA condition of 150 ℃/500 hours, is preferably at least 60,70,80 and 90%.
On the other hand, the present invention relates to above-disclosed daiamid composition is applied for high temperature.
On the other hand, the present invention relates to by thermoplastic compounds moulding of the present invention being manufactured to the method for goods.The example of goods is film or veneer sheet, automotive component or engine parts or electrical/electronic components.So-called " moulding " refers to any forming technique, for example extrusion molding, injection moulding, thermoforming molding, compression moulding or blowing.Preferably by injection moulding or blowing, form goods.
The multiple motor vehicle assembly of one or more during molding disclosed herein or extruded thermoplastic goods require below can being applied to meet: the polarity chemical such as zinc chloride and calcium chloride is had to very strong chemical resistance, the HI high impact requirement; High temperature resistant; Oil-proofness and fuel environment; Chemical-resistant reagent, as refrigerant; Low fuel and gas (as carbonic acid gas) perviousness.Concrete extrusion molding or molded thermoplastic product are selected from the pipeline for delivery of liquids and gases, liner, burning line, air brake pipe, main coolant pipe, air line, gas dynamic tube, hydraulic pressure housing, cable joint-box, junctor, tank and the plug-type cable of pipeline.Other non-automotive applications can be binding band and electrical/electronic junctor.
The present invention also is further detailed by following examples.Should be appreciated that following examples, only for illustration purpose, are not limited to the present invention.
Embodiment
method
chemical combination method A
Assign to prepare by listed one-tenth in melt blending table in 30mm twin screw extruder (ZSK 30 that Coperion manufactures) embodiment and the comparing embodiment of using PA 6T/DT, during operation, the cylinder set temperature of twin screw extruder is approximately 310 ℃, screw speed used is about 300rpm, throughput is 13.6kg/h, and the melt temperature manually recorded is approximately 355 ℃.By screw rod side feeding machine, glass fibre is added to this melt.One-tenth component shown in table all is based on the weight percent that accounts for the thermoplastic compounds gross weight and provides.
Extrude the mixture of chemical combination with the form of lace or strand, put into water-bath cooling, then be cut into particle and put into the aluminum liner sack of sealing, to prevent from absorbing moisture.Guarantee that by adjusting cooling and cutting condition the moisture content of material remains on the level lower than 0.15 % by weight.
physical property is measured
According to ISO 527-2/1A measurement mechanical tensile properties, i.e. E-modulus, rupture stress (tensile strength) and breaking strain (elongation at break).ISO stretching rod to injection moulding is measured.The molding temperature of PA6T/DT specimen is 145 to 150 ℃; Melt temperature is 325 to 330 ℃.
According to ISO 527/1A, used thickness is that the test rod that 4mm and width are 10mm is measured tensile strength and elongation under the test speed of 5 mm/min.Measure tensile modulus under the speed of 1 mm/min.
The testing method A tested with notched izod with ASTM D256 measures anti-notched Izod impact strength.
hot air box aging (AOA)
Test rod is put into to recirculation hot air box (Heraeus type UT6060), according to the operation described in detail in ISO2578, carry out thermal ageing.In a plurality of thermal aging time, take out test rod from baking oven, allow it be cooled to room temperature and be sealed in the aluminum liner sack in order to test.Then according to ISO 527 use Zwick stretching apparatus measures stretched mechanical characteristics.Provided the mean value obtained with 5 samples in table.
The retention rate of tensile strength (TS) and elongation at break (EL) is equivalent to the per-cent that 500 hours tensile strengths after thermal ageing and elongation at break are compared and drawn with the tensile strength that contrasts rod and elongation at break (can be considered 100%).The contrast rod has and test rod similarly forms and shape, but that test is dry state mo(u)lded item (DAM), and is not placed under the AOA condition.
material
pA6T/DTrefer to HTN501 NC010, it is the copolyamide of terephthalic acid, hexamethylene-diamine and 2-methyl-five methylene diamine, it has limiting viscosity (IV) in 0.8 to 0.95 (being generally 0.88) scope of recording according to ASTM D2857 method and the about fusing point of 300 ℃, can derive from E.I.DuPont de Nemours and Company (Wilmington, Delaware, USA).
copper is thermally-stabilisedagent refers to 7 parts of potassiumiodides and the mixture of 1 part of cupric iodide in 0.5 part of stearate cerul tackiness agent.
hindered amine refers to 4,4 ' bis-(alpha, alpha-dimethylbenzyl) pentanoic, can be commercially available from UniroyalChemical Company (Middlebury, Conn).
oP waxfor the lubricant of being manufactured by Clariant Corp. (Charlotte, NC).
embodiment 1
The PA6T/DT composition and the comparing embodiment C-1 to C-6 that do not strengthen of the embodiment 1 with EVOH have been listed in table 1.Tensile properties and reserved elongation at break % after under being placed in the AOA condition of 150 ℃/500h list in table 1.
Comprise EVOH (Soarnol
the A polymkeric substance) and secondary arylamines (Naugard
the embodiment 1 of combination 445 stablizers) shows the reserved elongation at break with 91% after 150 ℃ of lower AOA expose 500h.
The thermal stability of embodiment 1 is considerably beyond the thermal stability of all comparing embodiment C-1 to C-6 under identical exposure condition.For example:
The C-1 that only comprises EVOH shows the retention rate with 15%;
The C-2 that comprises known copper stablizer shows the retention rate with 72%;
Do not have the C-3 of stablizer to show the retention rate with 9%;
Only comprise secondary arylamines (Naugard
445 stablizers) C-4 shows the retention rate with 14%;
C-5 and C-6 with low molecular weight polyols show respectively the retention rate with 24% and 34%.These results are wondrous and beyond thought, and it clearly illustrates that poly-hydroxy polymer has excellent thermal stability while combining use with co-stabilizer in daiamid composition.
table 1
In all tables: the TS=tensile strength; The EL=elongation at break
Claims (9)
1. the thermoplastic article of molding or extrusion molding, described thermoplastic article comprises polyamide thermoplastic compositions, and described polyamide thermoplastic compositions comprises
(a) there is the polyamide resin of fusing point and/or glass transition point;
(b) one or more polyhydroxylated polymers of 1 to 7 % by weight, described polyhydroxylated polymer is selected from the ethylene/vinyl alcohol copolymer of the number-average molecular weight with at least 2000;
(c) one or more co-stabilizers of 0.1 to 3 % by weight, if the described fusing point of polymeric amide exists, described co-stabilizer has the low 10% weight loss temperature more than 30 ℃ of the described fusing point of ratio of measuring with thermogravimetric analysis, if perhaps described fusing point does not exist, described co-stabilizer has the 10% weight loss temperature of at least 250 ℃, and described co-stabilizer is selected from secondary arylamines, hindered amine as light stabilizer, hindered phenol and their mixture;
(d) 0 to one or more tougheners that are less than 10 % by weight; With
(e) the polymer toughening agent of 0 to 20 % by weight, the metal-salt that described polymer toughening agent comprises active function groups and/or carboxylic acid;
Wherein with the elongation at break that does not expose contrast of same composition and shape, compare, be exposed under the probe temperature of 150 ℃ the test duration of 500 hours in air atmosphere, and tested according to ISO 527-2/1A, the 4mm molding test rod prepared by described daiamid composition has average at least 50% reserved elongation at break; And
Wherein said polyamide resin comprises one or more polymeric amide, described polymeric amide independently selected from:
(III) organizes polymeric amide, and it has the described fusing point of at least 210 ℃, and comprises
(aa) half aromatic repeating units of 20 to 35 % by mole, described half aromatic repeating units is derived from being selected from following one or more monomer:
I. the aromatic dicarboxylate and the aliphatic diamine with 4 to 20 carbon atoms that there are 8 to 20 carbon atoms; And
(bb) the aliphatic repeating unit of 65 to 80 % by mole, described aliphatic repeating unit is derived from being selected from following one or more monomer:
Ii. the aliphatic dicarboxylic acid and the described aliphatic diamine with 4 to 20 carbon atoms that there are 6 to 20 carbon atoms; And
Iii. the lactan and/or the aminocarboxylic acid that there are 4 to 20 carbon atoms; And
(IV) organizes polymeric amide, and it comprises
(cc) half aromatic repeating units of 50 to 95 % by mole, described half aromatic repeating units is derived from being selected from following one or more monomer:
I. the aromatic dicarboxylate and the aliphatic diamine with 4 to 20 carbon atoms that there are 8 to 20 carbon atoms; And
(dd) the aliphatic repeating unit of 5 to 50 % by mole, described aliphatic repeating unit is derived from being selected from following one or more monomer:
Ii. the aliphatic dicarboxylic acid and the described aliphatic diamine with 4 to 20 carbon atoms that there are 6 to 20 carbon atoms; And
Iii. the lactan and/or the aminocarboxylic acid that there are 4 to 20 carbon atoms; And
(V) organizes polymeric amide, and it has the described fusing point of at least 260 ℃, and comprises
(ee) be greater than half aromatic repeating units of 95 % by mole, described half aromatic repeating units is derived from being selected from following one or more monomer:
I. the aromatic dicarboxylate and the aliphatic diamine with 4 to 20 carbon atoms that there are 8 to 20 carbon atoms; And
(ff) be less than the aliphatic repeating unit of 5 % by mole, described aliphatic repeating unit is derived from being selected from following one or more monomer:
Ii. the aliphatic dicarboxylic acid and the described aliphatic diamine with 4 to 20 carbon atoms that there are 6 to 20 carbon atoms; And
Iii. the lactan and/or the aminocarboxylic acid that there are 4 to 20 carbon atoms.
2. the thermoplastic article of the molding of claim 1 or extrusion molding, wherein said polyamide resin comprises the blend that (II) group and (V) organize polymeric amide, wherein (II) group polymeric amide has the described fusing point of at least 210 ℃, and comprise and be selected from following aliphatic polyamide: poly-(hexanedioyl butanediamine) (PA46), gather (ε-caprolactam) (PA6), it is poly-that (hexamethylene adipamide/(ε-caprolactam /) (PA66/6), gather (hexamethylene adipamide) (PA66), gather (hexamethylene adipamide/sebacoyl hexanediamine) (PA66/610), gather (hexamethylene adipamide/dodecane two acyl hexanediamines) (PA66/612), gather (hexamethylene adipamide/sebacoyl decamethylene diamine) (PA66/1010), gather (sebacoyl hexanediamine) (PA610), gather (dodecane two acyl hexanediamines) (PA612), gather (tetradecane two acyl hexanediamines) (PA614), gather (n-Hexadecane two acyl hexanediamines) (PA616), and poly-(hexanedioyl butanediamine/hexanedioyl 2 methyl pentamethylenediamine) (PA46/D6).
3. the thermoplastic article of the molding of claim 2 or extrusion molding, wherein said polyamide resin comprise comprise poly-(hexamethylene adipamide) (PA66) with poly-(hexamethylene terephthalamide/paraphenylene terephthalamide's 2 methyl pentamethylenediamine) blend (PA6T/DT).
4. the thermoplastic article of the molding of claim 1 or extrusion molding, wherein said one or more polyhydroxylated polymers comprise the ethylene/vinyl alcohol copolymer, and have the vinyl alcohol content of 40 to 75 % by mole, and wherein remaining % by mole is ethylene content.
5. the thermoplastic article of the molding of claim 1 or extrusion molding, wherein said at least one co-stabilizer is one or more secondary arylaminess.
6. the thermoplastic article of the molding of claim 1 or extrusion molding, wherein said at least one co-stabilizer is one or more hindered phenols.
7. the thermoplastic article of the molding of claim 1 or extrusion molding, wherein said daiamid composition comprises the copper that is less than 25ppm with Atomic Absorption Spectrometry.
8. the thermoplastic article of the molding of claim 1 or extrusion molding, wherein said goods are selected from pipeline, pipe lining, hydraulic pressure housing, cable joint-box, binding band, the junctor that comprises the electrical/electronic junctor, tank and the plug-type cable of carrying liquids and gases.
9. the thermoplastic article of the molding of claim 8 or extrusion molding, the pipeline of wherein said conveying liquids and gases is selected from burning line, air brake pipe, main coolant pipe, air line and gas dynamic tube.
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| US13734508P | 2008-07-30 | 2008-07-30 | |
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| US61/137,345 | 2008-07-30 | ||
| PCT/US2009/052231 WO2010014795A1 (en) | 2008-07-30 | 2009-07-30 | Thermoplastic articles including polyhydroxy polymers |
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| CN102112551B true CN102112551B (en) | 2013-11-06 |
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| CN2009801299732A Expired - Fee Related CN102112527B (en) | 2008-07-30 | 2009-07-30 | Heat resistant thermoplastic articles including co-stabilizers |
| CN2009801299747A Pending CN102112545A (en) | 2008-07-30 | 2009-07-30 | Copolyetherester compositions and articles made from these |
| CN2009801298227A Active CN102112526B (en) | 2008-07-30 | 2009-07-30 | Long-term heat aging resistant polyamide compositions |
| CN2009801297741A Pending CN102112550A (en) | 2008-07-30 | 2009-07-30 | Heat resistant thermoplastic articles |
| CN2009801297737A Expired - Fee Related CN102112549B (en) | 2008-07-30 | 2009-07-30 | Heat resistant thermoplastic articles including polyhydroxy polymers |
| CN2009801298157A Active CN102112525B (en) | 2008-07-30 | 2009-07-30 | Heat resistant molded or extruded thermoplastic articles |
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| CN2009801299732A Expired - Fee Related CN102112527B (en) | 2008-07-30 | 2009-07-30 | Heat resistant thermoplastic articles including co-stabilizers |
| CN2009801299747A Pending CN102112545A (en) | 2008-07-30 | 2009-07-30 | Copolyetherester compositions and articles made from these |
| CN2009801298227A Active CN102112526B (en) | 2008-07-30 | 2009-07-30 | Long-term heat aging resistant polyamide compositions |
| CN2009801297741A Pending CN102112550A (en) | 2008-07-30 | 2009-07-30 | Heat resistant thermoplastic articles |
| CN2009801297737A Expired - Fee Related CN102112549B (en) | 2008-07-30 | 2009-07-30 | Heat resistant thermoplastic articles including polyhydroxy polymers |
| CN2009801298157A Active CN102112525B (en) | 2008-07-30 | 2009-07-30 | Heat resistant molded or extruded thermoplastic articles |
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